CN101300707A - High durability fuel cell components with cerium oxide additives - Google Patents

High durability fuel cell components with cerium oxide additives Download PDF

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Publication number
CN101300707A
CN101300707A CNA2006800404140A CN200680040414A CN101300707A CN 101300707 A CN101300707 A CN 101300707A CN A2006800404140 A CNA2006800404140 A CN A2006800404140A CN 200680040414 A CN200680040414 A CN 200680040414A CN 101300707 A CN101300707 A CN 101300707A
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polymer dielectric
fuel cell
cerium oxide
electrode assembly
membrane electrode
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马修·H·弗雷
丹尼尔·M·皮尔庞特
史蒂文·J·汉罗克
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/49115—Electric battery cell making including coating or impregnating

Abstract

A fuel cell membrane electrode assembly is provided comprising a polymer electrolyte membrane which comprises a highly fluorinated polymer electrolyte and at least one cerium oxide compound dispersed therein. In addition, a method of making a fuel cell polymer electrolyte membrane is provided comprising the steps of: a) providing a highly fluorinated polymer electrolyte comprising acidic functional groups; b) dispersing therein at least one cerium oxide in an amount so as to provide between 0.01 and 5 percent of the total weight of the polymer electrolyte membrane; and c) thereafter forming a polymer electrolyte membrane comprising said polymer electrolyte.

Description

The high durability fuel cell components that contains cerium oxide additives
The present invention finishes under the support of government according to the cooperation agreement DE-FC36-02AL67621 that Ministry of Energy (DOE) authorizes.Government has some right to the present invention.
Technical field
The present invention relates to show the fuel cell membrane electrode assembly of increased durability and contain fuel cell polymer electrolyte membrane of cerium oxide and preparation method thereof.
Background technology
It is said that US 6,335,112 (Asukabe) disclose a kind of polymer dielectric film that comprises the alkyl solid polymer electrolyte that contains catalyst that can decompose hydroperoxide.This reference paper is offered the multiple element that has proposed to be used for described catalyst.
It is said that US 2003/0008196 (Wessel) discloses a kind of fuel cell electrode that comprises the catalyst of decompose hydroperoxide.This list of references has proposed to be used for the multiple element of described catalyst.
It is said that US 2002/0093008 and US 2004/0251450 (Kerres) disclose a kind of complexes membrane that comprises the osmotic ceramic nanoparticle network of the nano sized particles that is used for proton conduction.
Tetrafluoroethene (TFE) and use chemical formula: FSO 2-CF 2-CF 2-O-CF (CF 3)-CF 2-O-CF=CF 2The copolymer of comonomer be known and by DuPontChemical Company, Wilmington, Delaware is with trade name
Figure A20068004041400061
Sell, the sale form is a sulfonic acid, that is, and and FSO wherein 2-end group is hydrolyzed to HSO 3-). Generally be used to make the polymer dielectric film that fuel cell uses.
Tetrafluoroethene (TFE) and use chemical formula: FSO 2-CF 2-CF 2-O-CF=CF 2The copolymer of comonomer also be known and when manufacturing is used for the polymer dielectric film of fuel cell, be sulphonic form, be i.e. FSO wherein 2-end group is hydrolyzed to HSO 3-.
The U.S. Patent application No.10/325 that submits on December 19th, 2002,278 disclosure is incorporated herein with way of reference, this patent disclosure 90 microns of a kind of thickness or littler and polymer dielectric film that contain a kind of polymer, described polymer contains the highly fluorinated main chain and the repeating side groups of with good grounds following chemical formula:
YOSO 2-CF 2-CF 2-CF 2-CF 2-O-[main polymer chain]
Wherein Y is H +Or such as the univalent cation of alkali metal cation.Typically, described film is a casting film.Typically, described polymer has the hydrated product greater than 22,000.Typically, described polymer has 800 to 1200 equivalent.
Summary of the invention
In brief, the invention provides a kind of fuel cell membrane electrode assembly that contains polymer dielectric film, described polymer comprises highly fluorinated polymer dielectric and at least a dispersion cerium oxide compound wherein.Typically, evenly distribute in whole described polymer dielectric film thickness cerium oxide compound.Typically, evenly distribute at whole described polymer dielectric film thickness polymer dielectric.Typically highly fluorinated polymer dielectric is fluoridized.Typically with respect to the total weight of polymer dielectric film, the amount of cerium oxide is between 0.01 weight % and 5 weight %, more typically between 0.1 weight % and 1 weight %.And the most typically between 0.2 weight % and 0.3 weight %.Typically with respect to the cumulative volume of polymer dielectric film, the amount of cerium oxide is less than 1 volume %, more typically less than 0.8 volume %, and more typically less than 0.5 volume %.Cerium oxide can be CeO 2Cerium oxide can be Ce 2O 3Typically, polymer dielectric has 1000 or littler, and more typical 900 or littler, and more typical 800 or littler equivalent.Polymer dielectric can comprise the side group according to following chemical formula :-O-CF 2-CF 2-CF 2-CF 2-SO 3H is perhaps according to the side group of following chemical formula :-O-CF 2-CF (CF 3)-O-CF 2-CF 2-SO 3H.
On the other hand, the invention provides a kind of method for preparing fuel cell polymer electrolyte membrane, said method comprising the steps of: the highly fluorinated polymer dielectric that contains acidic functionality a) is provided; B) dispersion at least a cerium oxide wherein, the amount of described cerium oxide is between 0.01% and 5% polymer dielectric film total weight; And c) forms the polymer dielectric film that contains described polymer dielectric then.Typically, be evenly distributed at whole described polymer dielectric film thickness cerium oxide.Typically, be evenly distributed at whole described polymer dielectric film thickness polymer dielectric.Typically highly fluorinated polymer dielectric is fluoridized.Typically with respect to the total weight of polymer dielectric film, the cerium oxide amount is between 0.01 weight % and 5 weight %, more typically between 0.1 weight % and 1 weight %, and the most typically between 0.2 weight % and 0.3 weight %.Typically with respect to the cumulative volume of polymer dielectric film, the cerium oxide amount is less than 1 volume %, more typically less than 0.8 volume %, and more typically less than 0.5 volume %.Cerium oxide can be CeO 2Cerium oxide can be Ce 2O 3Typically polymer dielectric has 1000 or littler, and more typical 900 or littler, and more typical 800 or littler equivalent.Polymer dielectric can comprise the side group according to following chemical formula :-O-CF 2-CF 2-CF 2-CF 2-SO 3H is perhaps according to the side group of following chemical formula :-O-CF 2-CF (CF 3)-O-CF 2-CF 2-SO 3H.
On the other hand, the invention provides a kind of method for preparing fuel cell membrane electrode assembly, described method comprises that this paper is used to prepare any method of polymer dielectric film, and may further comprise the steps in addition: d) form the membrane electrode assembly that contains that polymer dielectric film.
In present patent application:
In the polymer film " evenly " of additive distribute refer to the additive capacity that exists change be no more than+/-90%, more typical being no more than+/-50%, and more typical being no more than+/-20%;
" equivalent " of polymer (EW) refer to in and the polymer weight of monovalent alkali;
" polyvalent cation " refers to have the 2+ or the cation of large charge more.
" highly fluorinated " refer to fluorinated volume be 40 weight % or more than, typically 50 weight % or more than, and more typically 60 weight % or more than; With
" sour form " refers to the form that neutralized by proton, and it is relevant with the anionic functional group.
Of the present invention advantage provides a kind of fuel cell membrane electrode assembly that increased durability is provided and polymer dielectric film and preparation method thereof.
Description of drawings
Fig. 1 is the figure of the fuel cell test result in useful life of four kinds of membrane electrode assemblies of report (MEA), cell voltage potential (the trace A1 that comprises example 9C comparison MEA, the left-hand scale chi), the cell voltage potential of two example 10MEA of the present invention (trace C1 and D1, the left-hand scale chi), cell voltage potential (the trace B1 that contains the comparison MEA of Mn salt additives, the left-hand scale chi), fluorine ion rate of release (the trace A2 of example 9C comparison MEA, the right side ruler), fluorine ion rate of release (trace C2 and the D2 of two kinds of example 10MEA of the present invention, the right side ruler), fluorine ion rate of release (trace B2, right side ruler) with the comparison MEA that contains the Mn salt additives.
Embodiment
The invention provides a kind of fuel cell membrane electrode assembly that contains polymer dielectric film, described film comprises highly fluorinated or fluoridized polymer dielectric and disperses wherein at least a such as CeO 2Or Ce 2O 3Cerium oxide, wherein evenly distribute at whole polymer dielectric film thickness cerium oxide.
Can be used for electrochemical cell according to membrane electrode assembly of the present invention (MEA) or polymer dielectric film (PEM) such as fuel cell.MEA is the center part of Proton Exchange Membrane Fuel Cells such as hydrogen fuel cell.Fuel cell is an electrochemical cell, and its catalytic combination by fuel such as hydrogen and the oxidant such as oxygen produces available power.Typical MEA comprises polymer dielectric film (PEM) (being also referred to as ion-conductive membranes (ICM)), and its effect is a solid electrolyte.The face of PEM contacts with anode electrode layer, and opposite face contacts with negative electrode layer.In the typical case uses, form proton at the anode place via the oxidation of hydrogen, and pass PEM it is transferred to negative electrode, with oxygen reaction, electric current is flowed in the external circuit that connects two electrodes.Each electrode layer includes electrochemical catalyst, and catalyst generally includes platinum.PEM forms durable, atresia, non-conductive mechanical masking between reacting gas, yet it also transmits H easily +Ion.Gas diffusion layers (GDL) helps the transmission and the conduction current of gas turnover anode and cathode electrode material.GDL is a porous, conducts electricity again, and is made up of carbon fiber usually.GDL also can be called as fluid transport layer (FTL) or diffuser/current collector (DCC).In certain embodiments, anode and negative electrode layer be administered to GDL goes up and the GDL and the PEM of the catalyst coated of gained clip together, form five layers MEA.Five layers of five layers MEA are followed successively by: anode GDL, anode electrode layer, PEM, negative electrode layer and negative electrode GDL.In other embodiments, anode and negative electrode layer are applied in the either side of PEM, the catalyst coated membrane (CCM) with gained is clipped between two GDL then, forms five layers MEA.
Can comprise any suitable polymers electrolyte according to PEM of the present invention.Can be used for the anionic functional group that polymer dielectric of the present invention has the common backbone of being bonded to usually.These functional groups are generally sulfonic acid group, but also can comprise hydroxy-acid group, imide group, amide group or other acidic functionalities.It is highly fluorinated can be used for polymer dielectric of the present invention, and typically is fluoridized most.Can be used for the copolymer that polymer dielectric of the present invention is generally the comonomer of tetrafluoroethene and one or more sour official's energy of fluoridizing.Typical polymer dielectric comprises
Figure A20068004041400101
(DuPont Chemicals, Wilmington DE) and Flemion TM(Asahi Glass Co.Ltd., Tokyo, Japan).Polymer dielectric can be tetrafluoroethene (TFE) and FSO 2-CF 2CF 2CF 2CF 2-O-CF=CF 2Copolymer, U.S. Patent application 10/322,254,10/322,226 and 10/325,278 is seen in its description, these patent applications are incorporated herein by reference.Described polymer has 1200 or littler usually, and more typically 1100 or littler equivalent (EW).In certain embodiments, can use to have unusual low EW typically 1000 or littler, more typically 900 or littler, and more typically 800 or littler, polymer, have the polymer phase ratio of higher EW with use, these embodiment usually have the performance of improvement.Wish not to be bound by theory, it is believed that cerium oxide can and form the crosslinked strength polymer that adds by chelating between the anionic group of bonding.
Can make polymer form film by any suitable method.Typically, polymer is the foundry goods of suspension.Can use any suitable pouring procedure, comprise that rod is coated with, sprays, stitches and be coated with, brush, and similar approach.Alternatively, can utilize that smelting process forms film from straight polymer such as extruding.Typically, after forming, can utilize 120 ℃ or more than, more typically utilize 130 ℃ or more than, the most typically utilizing 150 ℃ or above temperature is described film annealing.Typically, the thickness of PEM more typically less than 40 microns, more typically less than 30 microns, and is 25 microns less than 50 microns approximately.Typically, be evenly distributed, that is to say, do not interrupted by the carrier structure of any interpolation at whole described polymer dielectric film thickness polymer dielectric.
In one embodiment of the invention, before film forms, will be such as CeO 2Or Ce 2O 3And so on, but more typically with CeO 2One or more cerium oxide compound be scattered in the polymer dielectric.Cerium oxide compound can be crystallization or amorphous.Cerium oxide compound can comprise (IV) oxidation state, (III) oxidation state or both ceriums.In one embodiment, cerium oxide compound is substantially free of metallic cerium.Alternatively, cerium oxide compound can both comprise cerium oxide, comprised metallic cerium again.Alternatively, cerium oxide compound can be used as very thin oxidation reaction product layer and is bearing on the metallic cerium particle.In one embodiment, cerium oxide compound can not comprise other metallic element substantially.Alternatively, cerium oxide compound can comprise other metallic element, and therefore can be considered the mixed-metal oxides compound that contains cerium oxide.The mixed-metal oxides examples for compounds that contains cerium oxide comprises solid solution and the multi-component oxide compound such as cerium acid barium such as zirconia-ceria.Cerium oxide compound is fully mixed with polymer dielectric, realize distributing uniformly substantially.Realize mixing by any suitable method, comprise grinding, mediate and similar method, and can under the situation that comprises or do not comprise solvent, carry out.In final polymer dielectric or PEM total weight, the amount of the cerium oxide compound of interpolation is usually between 0.0 weight % and 5 weight %, more typically between 0.1 weight % and 2 weight %, and more typically between 0.2 weight % and 0.3 weight %.Typically, with respect to the cumulative volume of polymer dielectric film, the cerium oxide compound amount is less than 1 volume %, more typically less than 0.8 volume %, and more typically less than 0.5 volume %.Cerium oxide can be the particle of any suitable dimension, typically 1 and 5000nm between.In certain embodiments, preferred size 200 is to 5000nm.In certain embodiments, preferred size 500 is to 1000nm.
In order to prepare MEA or CCM, can catalyst be applied on the PEM by any suitable method, comprise craft and mechanical means, comprise that manual brush, notch bar are coated with, the FDB mould is coated with, the wire-wound rod is coated with, FDB coating, slot-fed blade coating, three roller coat apply or decal transfer.Can utilize once coating or repeatedly coating realization coating.
Any appropriate catalyst can be used for the present invention's practice.Typically, use carbon-supported catalyst particles.By weight, typical carbon-supported catalyst particles is the carbon of 50-90% and the catalyst metals of 10-50%, and typically catalyst metals comprises that the weight rate that is used for negative electrode Pt and is used for anode is 2: 1 Pt and Ru.Typically, the catalyst with the catalyst ink form is administered on PEM or the FTL.Alternatively, catalyst ink can be administered on the transfer substrate, dry, and be administered to PEM as applique subsequently or to FTL.Typically catalyst ink comprises polymer electrolyte, and this material can be identical or different with the polymer electrolyte that comprises PEM.Typically catalyst ink comprises the catalyst granules dispersion that is arranged in the polymer dielectric dispersion.Typically ink comprises the solid (being polymer and catalyst) of 5-30%, and more typically comprises the solid of 10-20%.Electrolyte dispersion is generally aqueous dispersion, and described dispersion can comprise alcohol and the polyalcohol such as glycerine and ethylene glycol in addition.Can adjust the content of water, pure and mild polyalcohol, thereby change the rheological characteristic of ink.Typically described ink comprises the polyalcohol of the pure and mild 0-20% of 0-50%.In addition, ink can comprise the suitable dispersant of 0-2%.Typically by stirring in heating, the method that is diluted to the denseness that can apply is subsequently made ink.
Can comprise porous supporting mass such as expansion PTFE layer and similar material in addition according to PEM of the present invention, wherein the hole of porous supporting mass comprises polymer dielectric.Can not comprise the porous supporting mass according to PEM of the present invention.Can comprise cross-linked polymer according to PEM of the present invention.
In order to prepare MEA, can GDL be administered to the either side of CCM by any suitable method.Any suitable GDL can be used for the present invention's practice.Typically GDL is made of the sheeting that contains carbon fiber.Typically GDL is selected from the carbon fiber constructions of weaving with the non-woven carbon fiber structure.The carbon fiber constructions that can be used for the present invention's practice can comprise: Toray TMCarbon paper, SpectraCarb TMCarbon paper, AFN TMNon-woven carbon cloth, Zoltek TMCarbon cloth or the like.Can be with coating of multiple material or dipping GDL, these materials comprise carbon granules coating, hydrophilic treated product and such as the hydrophobic treatment product of coating polytetrafluoroethylene (PTFE).
Typically, in use, MEA according to the present invention is clipped between two rigid plate, and described plate is known as distribution plate, also is known as bipolar plate (BPP) or unipolar plates.Similar with GDL, distribution plate must conduct electricity.Typically distribution plate is by carbon composite, metal, or plated metal material is made.Typically distribution plate is via the reactant or the product fluid that pass in and out the MEA electrode surfaces in engraving in (one or more) surface of (one or more) MEA, grinding, one or more conducting fluid channel allocations molded or compacting.These passages are referred to as the flow field sometimes.Distribution plate can distribute the fluid that passes in and out two stacked continuous N EA, and one of them face is guided fuel the anode of first MEA into, and another face is guided oxidant the negative electrode (and removing product water) of next MEA into, thereby uses term " bipolar plate ".Alternatively, distribution plate can only have passage in a side, only is distributed in the fluid of that side turnover MEA, and it can use term " unipolar plates ".When being used for this area, typically, the term bipolar plate also comprises unipolar plates.A typical fuel battery comprises some and the alternately laminated MEA of bipolar plate.
The present invention can be used for the manufacturing and the operation of fuel cell.
Below example further specify target of the present invention and advantage, but the concrete material in these examples, narrated and and quantity, and other condition and details all should not be construed as improper restriction of the present invention.
Example
Unless otherwise noted, otherwise all reagent be all available from maybe can deriving from Aldrich ChemicalCo., Milwaukee, and WI maybe can be synthetic by known method.
Film preparation
The ionomer that is used for following each example is the copolymer of tetrafluoroethene (TFE) and FSO2-CF2CF2CF2CF2-O-CF=CF2 (comonomer A).Prepare comonomer A according to U.S. Patent application 10/322,254 and 10/322,226 disclosed step, described patent is incorporated herein with way of reference.Of U.S. Patent application 10/325,278, carry out polymerization by the water and milk polymerization reaction.Equivalent (EW) is 1000 (ion-exchange capacities: 0.001 moles per gram).Utilize cast solution that ionomer is provided, described cast solution comprised 22.3% solid in the n-propanol/water at 70: 30.Cast solution comprises the iron of content less than 1ppm.The method for preparing film is to utilize the gap applicator more than 4 inches in gap 0.020 inch (0.0508cm) (Columbia Maryland) is cast in dispersion on the glass pane by hand shop technology for catalog number PAR-5357, BYK-Gardner.Make film in surrounding air dry 15 minutes, then in 80 ℃ air-oven dry 10 minutes, heating 15 minutes in 200 ℃ air-oven subsequently.
Peroxide soak test
Oxidation stability to the perfluorinated ionomers film for preparing in a plurality of examples is tested, and method is as follows.The careful membrane sample of weigh between 0.03g and 0.06g is immersed in them the 50g hydrogenperoxide steam generator (initial concentration 1M) that is arranged in glass jar then.Seal this wide-mouth bottle, and it was placed in 90 to 95 ℃ the baking oven 5 days.After 5 days the soak period, from solution, take out sample.Use rinsed with deionized water, at room temperature drying is at least three hours, and weighs.Calculate original loss in weight numeral.In order to retrain before the immersion that the envionmental humidity that is attributable between 0 day and 5 days changes and afterwards weight difference, last a slice of each membrane sample of weighing in addition when beginning and between soak period (that is never be exposed to peroxide) sample.For the loss in weight reading that obtains proofreading and correct, the weight fraction of at first using unsoaked diaphragm " to stay " is removed the calculating numeral of the original weight mark that stays after (immersion sample) soaks.Back one is handled and is supposed that it is its several times to the deviation effect of the immersion sample actual measurement loss in weight that relative humidity changes the weight change effect that causes.
Acid content is measured
Carry out titration, determine ionomeric membrane acid content with the method preparation of adding the ion cerium.In each titration, all the sample of ionomer film of the careful about 0.05g of weighing adds it in 0.1M NaCl solution of 100ml.With buret 0.05M NaOH solution is slowly added in the sample solution, determine terminal point with pH meter.Utilize the required NaOH scale of neutralizing acid to show the acid content of film.
MEA makes
Preparation effective area 50cm 2Fuel cell membrane electrode assembly (MEA), method is as follows.Method according to WO 2002/061,871 explanation prepares catalyst dispersion, and this document is incorporated herein by reference.In order to prepare catalyst coated membrane, the decal transfer method that illustrates according to same list of references WO 2002/061,871 is administered to anode layer and cathode layer on the film.Carbon paper gas diffusion layers and polytetrafluoroethylene/glass composite gaskets that PTFE is handled are administered on the CCM, and method is that (Fred Carver Co., Wabash made 10 minutes with defeating of 13.4kN in IN) for Carver press at 132 ℃.
MEA tests useful life
Has the independently test station of gas flow, pressure, relative humidity, curtage controller (Fuel Cell Technologies, Albuquerque, New Mexico) test MEA.Test fixture comprises having four graphite current collector plates of spiraling the flow field.With the H under 90 ℃ the incomplete saturation conditions 2/ air operation MEA, wherein anode excess pressure.Make the test of MEA experience load of accelerating cycle life by the method that applies multiple different current density values.After each duty cycle, all measure and write down the open circuit voltage (OCV) of battery.For OCV, the general phenomenon of this testing scheme is a monotonic decay, but has obviously " flex point " or significantly improve on rate of decay.The point that utilizes rate of decay to improve is represented the useful life of MEA.Alternatively, can select to indicate the terminal point in useful life of MEA than threshold voltage value.Also can flow out the rate of release of fluorine ion in the water by the ion chromatography measurement fuel cell operation.Higher fluoride rate of release shows the very fast degraded of fluoro-containing copolymer film.
Comparative example 1C
Prepare control film according to above-mentioned detailed description, different is that the cast dispersion comprises the additional iron (in polymer weight 500ppm) that obtains with the method for adding ferric nitrate.With 0.081g ferric nitrate (Fe (NO 3) 3-9H 2O, production number I110-500, Fisher Scientific, Fair Lawn, New Jersey) add the ionomer cast dispersion of the 22.7 weight % of 99g, stirred simultaneously 24 hours.Described iron salt dissolved obtains limpid cast dispersion.According to above preset sequence casting film.The result that the peroxide soak test of table 1 report film and acid content are measured.Prepare two samples, reporting the result is the mean value of these two samples.
Example 2-4
Will be according to the cerium oxide (CeO of 10g aliquot with 0.5 to 1.0 granularity of different amounts of the cast dispersion of embodiment 1C preparation 2, " Polishing Opaline " is commercially available with trade name, Rhodia Electronics and Catalysis, and Cranbury, New Jersey makes) further combination, and stirred 24 hours.According to above preset sequence casting film.The result that the peroxide soak test of these films of table 1 report and acid content are measured.In example 2,3 and 4, each example all prepares two samples, reports the result to be the mean value of these two samples.
Table I
Example The CeO that adds 2 (g) CeO 2Weight % Peroxide soak test (change of % weight) Acid content (meq/g)
1C Do not have Do not have -14.5％ 1.02
2 0.0057 0.25 -5.3％ 0.99
3 0.0114 0.50 -3.7％ 0.99
4 0.0229 1.0 -3.0％ 0.95
The interpolation of cerium oxide reduces the loss in weight of perfluorinated ionomers consistently, shows the oxidation stability of higher degree.
Comparative example 5C
Prepare control film according to above-mentioned detailed description, different is that the cast dispersion comprises the additional iron (500ppm) that obtains with the method for adding ferric nitrate.With 0.081g ferric nitrate (Fe (NO 3) 3-9H 2O (production number I110-500, Fisher Scientific, Fair Lawn, New Jersey) joins the ionomer of the 22.7 weight % of 99g and pours into a mould in the dispersion, stirs simultaneously 24 hours.Described iron salt dissolved obtains limpid cast dispersion.According to above preset sequence casting film.The result that the peroxide soak test of Table II report film and acid content are measured.Prepare two samples, reporting the result is the mean value of these two samples.
Example 6
Make aliquot and cerium oxide (CeO according to the cast dispersion of example 5C preparation 2, production number 55322, Alfa Aesar, Ward Hill, Massachusetts) further combination, and stirred 24 hours.According to above preset sequence casting film.According to above preset sequence cast a slice film.The result that the peroxide soak test of Table II report film and acid content are measured.The interpolation of cerium oxide has reduced the loss in weight of perfluorinated ionomers, shows the oxidation stability of higher degree.
Table II
Example Peroxide soak test (change of % weight) Acid content (meq/g)
5C -9.5％ 1.00
6 -3.4％ 0.95
Comparative example 7C
The method of describing according to comparative example 1C prepares control film.The result of the peroxide soak test of Table III report film.Prepare two samples, reporting the result is the mean value of these two samples.
Example 8
Aliquot according to the polymer cast dispersion of example 5C preparation (measure the polymer of 23.3 weight % and comprise the iron of 500ppm) is further made up with water-based cerium oxide colloidal dispersion.With 0.0329g 20 weight %, the CeO of granularity 10 to 20nm 2(Ward Hill Massachusetts) adds the 5.28g polymeric dispersions to colloidal dispersion, stirs simultaneously for production number 12730, Alfa Aesar.With CeO 2With the gross mass meter of polymer, obtain the CeO of 0.53 weight % to improve quality 2Or 0.031meq Ce/g.Stir described mixture 8 hours, and obtained muddy cast dispersion.According to above preset sequence casting film.The result of the peroxide soak test of Table III report film.Prepare two samples, reporting the result is the mean value of these two samples.
Table III
Example Peroxide soak test (change of % weight)
7C -14.6％
8 -3.7％
Comparative example 9C
According to United States Patent (USP) 6,649, the method for 295 case description prepares control film, and this patent is incorporated herein by reference.
Example 10
Utilize as example 2 is described two kinds of films and process MEA as mentioned above as a kind of film of example 9C description.Fig. 1 reports the fuel cell test result in useful life of these MEA, cell voltage potential (the trace A1 that comprises example 9C comparison MEA, the left-hand scale chi), the cell voltage potential of two kinds of example 10MEA of the present invention (trace C1 and D1, the left-hand scale chi), fluorine ion rate of release (the trace A2 of example 9C comparison MEA, the right side ruler) and the fluorine ion rate of release of example 10MEA of the present invention (trace C2 and D2, right side ruler).In order to compare, Fig. 1 reports cell voltage potential and the fluorine ion rate of release (trace B1 and B2) of the comparison MEA that utilizes the preparation of Mn salt additives in addition.The drama that example 10MEA of the present invention shows useful life prolongs and fluorine ion discharges minimizing.
Concerning those skilled in the art, various modifications of the present invention and change will be conspicuous, but they do not deviate from scope of the present invention and principle, and should be appreciated that the present invention should not be subject to exemplary embodiment mentioned above undeservedly.

Claims (31)

1. fuel cell membrane electrode assembly, it comprises polymer dielectric film, described polymer dielectric film comprises highly fluorinated polymer dielectric and disperses wherein at least a cerium oxide compound.
2. fuel cell membrane electrode assembly according to claim 1, the wherein said highly fluorinated distribution of polymer dielectric on whole described polymer dielectric film thickness is uniformly, and the distribution of wherein said at least a cerium oxide compound on whole described polymer dielectric film thickness is uniform.
3. fuel cell membrane electrode assembly according to claim 1, wherein said highly fluorinated polymer dielectric is fluoridized.
4. fuel cell membrane electrode assembly according to claim 1, wherein with respect to the total weight of described polymer dielectric film, the amount of the existence of described at least a cerium oxide compound is between 0.01 weight % and 5 weight %.
5. fuel cell membrane electrode assembly according to claim 1, wherein with respect to the total weight of described polymer dielectric film, the amount of the existence of described at least a cerium oxide compound is between 0.01 weight % and 1 weight %.
6. fuel cell membrane electrode assembly according to claim 1, wherein with respect to the total weight of described polymer dielectric film, the amount of the existence of described at least a cerium oxide compound is between 0.2 weight % and 0.3 weight %.
7. fuel cell membrane electrode assembly according to claim 1, wherein with respect to the cumulative volume of described polymer dielectric film, the amount of the existence of described at least a cerium oxide compound is less than 1 volume %.
8. fuel cell membrane electrode assembly according to claim 1, wherein said at least a cerium oxide compound is CeO 2
9. fuel cell membrane electrode assembly according to claim 1, wherein said at least a cerium oxide compound is Ce 2O 3
10. fuel cell membrane electrode assembly according to claim 1, wherein said polymer dielectric have 1000 or littler equivalent.
11. fuel cell membrane electrode assembly according to claim 1, wherein said polymer dielectric have 900 or littler equivalent.
12. fuel cell membrane electrode assembly according to claim 1, wherein said polymer dielectric have 800 or littler equivalent.
13. fuel cell membrane electrode assembly according to claim 1, wherein said polymer dielectric comprises the side group according to following chemical formula:
-O-CF 2-CF 2-CF 2-CF 2-SO 3H。
14. fuel cell membrane electrode assembly according to claim 1, wherein said polymer dielectric comprises the side group according to following chemical formula:
-O-CF 2-CF(CF 3)-O-CF 2-CF 2-SO 3H。
15. a method for preparing fuel cell polymer electrolyte membrane said method comprising the steps of:
A) provide the highly fluorinated polymer dielectric that contains acidic functionality;
B) distribution of at least one cerium oxide compound therein, the amount of described cerium oxide compound is 0.01% to 5% of a described polymer dielectric film total weight; With
C) form the polymer dielectric film that contains described polymer dielectric then.
16. method according to claim 15, the wherein said highly fluorinated distribution of polymer dielectric on whole described polymer dielectric film thickness is uniformly, and wherein every kind of cerium oxide compound distribution on whole described polymer dielectric film thickness is uniform.
17. a method for preparing fuel cell membrane electrode assembly, described method comprises method according to claim 15, and may further comprise the steps in addition:
D) form the membrane electrode assembly that comprises described polymer dielectric film.
18. method according to claim 15, wherein said highly fluorinated polymer dielectric is fluoridized.
19. method according to claim 15, the amount of wherein said at least a cerium oxide compound are 0.1% to 1% of described polymer dielectric film total weight.
20. method according to claim 15, the amount of wherein said at least a cerium oxide compound are 0.2% to 3% of described polymer dielectric film total weight.
21. method according to claim 15, wherein with respect to the cumulative volume of described polymer dielectric film, the amount that described at least a cerium oxide compound exists is less than 1 volume %.
22. method according to claim 15, wherein said at least a cerium oxide compound is CeO 2
23. method according to claim 15, wherein said at least a cerium oxide compound is Ce 2O 3
24. method according to claim 15, wherein said polymer dielectric have 1000 or littler equivalent.
25. method according to claim 15, wherein said polymer dielectric have 900 or littler equivalent.
26. method according to claim 15, wherein said polymer dielectric have 800 or littler equivalent.
27. method according to claim 15, wherein said polymer dielectric comprises the side group according to following chemical formula:
-O-CF 2-CF 2-CF 2-CF 2-SO 3H。
28. method according to claim 15, wherein said polymer dielectric comprises the side group according to following chemical formula:
-O-CF 2-CF(CF 3)-O-CF 2-CF 2-SO 3H。
29. fuel cell membrane electrode assembly according to claim 1, described assembly comprises the porous supporting mass in addition.
30. fuel cell membrane electrode assembly according to claim 1, described assembly does not comprise the porous supporting mass.
31. fuel cell membrane electrode assembly according to claim 1, wherein said polymer is crosslinked.
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